BRPI0613348A2 - method for increasing the molecular weight of a polymer, method for increasing the molecular weight and providing branching in a polymer and polymer - Google Patents

Abstract

METHOD FOR INCREASING THE MOLECULAR WEIGHT OF A POLYMER, METHOD FOR INCREASING THE MOLECULAR WEIGHT AND PROVING BRANCHING IN A POLYMER AND POLYMER. The invention is a method for increasing the molecular weight of and optionally providing branching in a polymer having a first repeating unit, which comprises the residual of a condensation reaction of an aliphatic dicarboxylic acid with either a bis amide diol or a bis diamide diester , and a second repeating unit, which comprises the residual of a condensation reaction of a diol with an aliphatic dicarboxylic acid. The invention is also the branched polymer that can be prepared by such a method.

Description

"METHOD FOR INCREASING MOLECULAR WEIGHT OF A POLYMER, METHOD FOR INCREASING MOLECULAR WEIGHT AND PROVERRAMIFICATION IN A POLYMER AND POLYMER".

Invention History

The present invention relates to a process for increasing the molecular weight of an amide ester polymer.

USP 6,172,167 discloses tendobo amide ester polymers for mechanical and environmental properties. Patented '167 polymers consist of building blocks with the general structure - (CB-VB) - in which CB represents a constant length block and VB represents a variable length block. When the average molecular weight of the v167 polymeric composition is greater than 10,000 g / mol, then the polymeric compositions have increased strength, stiffness, elasticity and ductility properties exhibiting improved film and fiber forming properties. Patent process 167 produces larger molecular weight polymers by heating the polymers to promote chain condensation. However, the rate of chaincondensation decreases significantly as the molecular weight of the polymer increases. Therefore, it is time consuming to produce desirable high molecular weight polymers using the process of the λ167 patent. Accordingly, there remains a need for a simpler method for producing such increased molecular weight amide ester polymers.

Alternatively it may be desirable to either increase the pesomolecular or to produce branched high pesomolecular poly (ester-amides) using polyfunctional initiators but avoiding gelation of the composition.

Summary of the invention

Thus, according to a first embodiment, the present invention is a method for increasing the pesomolecular of a polymer having a first repeating unit comprising the residue of a condensation reaction or an aliphatic dicarboxylic acid with a diol bisamide or a diol with a diamide diester, a second repeating unit, comprising the oresidual of a condensation reaction of a diol and an aliphatic dicarboxylic acid, provided that at least one (and preferably one or the other but not both) dodiol or aliphatic dicarboxylic acid is characterized by when found independently in a reagent mixture they are volatile and can be separated from the reaction mixture by distillation. The polymer has a number average molecular weight of less than 2000g / mol. The polymer is combined with a reagent selected from the group consisting of nonvolatile diols (preferably when the polymer comprises a diolvolatile) and high boiling or long chain dicarboxylic acid (preferably when the polymer comprises the residual of an aliphatic volatile dicarboxylic acid and the polymer). does not comprise a volatile diol). The temperature is maintained at a level to increase the molecular weight to 4000 g / mol or more (preferably 6000 g / mol or more and more preferably 10,000 g / mol or more) and to replace at least part of the volatile groups ( diol or diacid) by the non-volatile reagent.

According to a second embodiment, the invention is a method for increasing molecular weight and proliferation in a polymer comprising a first repeating unit, which is the residual of a diol -condensing reaction and an aliphatic dicarboxylic acid where the polymer has a molecular weight of less than 200 g / mol. The polymer is combined with a reagent that is selected from polyols and polyacids (or depolyacid esters), wherein the reagent has at least three functional groups -OH, -ester, or -COOH as appropriate. The temperature is maintained at a sufficiently high level. form a branched polymer having a molecular weight of 4000 g / mol or more, preferably greater than 6000 g / mol, more preferably greater than 10,000 g / mol. According to a third embodiment the invention is a polymer that can be prepared according to the method. of the second incorporation.

Detailed Description of the Invention

Note that in the formulas shown in this specification oxygen in the repeating unit or portion of repeating units is represented as occurring at an end of the repeating unit or portion of repeating unit. However, oxygen may have been shown at the other end of the repeating unit or portion of the repeating unit and still represented on the same actual structure. Therefore, structures as shown herein will be recognized as representing both variants.

In the first embodiment, when the first repeating unit comprises residual of a bis amide diol and the second repeating unit comprises residual of a volatile diol, the first repeating unit may be represented by the structure: - [Hl-AA] -, where Hl is -R -CO-NH-Ra-NH-CO-RO- or -R-NH-CO-R-CO-NH-R-0- where Ra is R or a bond, at each occurrence R is independently an aliphatic or heteroaliphatic alicyclic group or heteroalicyclic or aromatic or heteroaromatic, preferably R is an aliphatic group of 1 to 10, preferably of 1-4 carbon atoms and AA is -CO-R'-CO-O where R 'is a bond or aliphatic group, preferably from 1 to 10 preferably from 2-4 carbon atoms. The second repeating unit may be represented by the formula - [DV-AA] -, where DV is - [R "-0] - eR" is an aliphatic or heteroaliphatic, alicyclic or heteroalicyclic or aromatic or heteroaromatic group selected such that R "(OH) 2 may be distilled from the reaction mixture. Preferably R 'is an aliphatic group of 1 to 8, more preferably 2 to 4 carbon atoms. The molecular weight of the polymer is less than 2000g / mol.

Thus, according to one embodiment the polymer may be represented as having the formulaHO-D1-O- [-CO-AA1-COO-D1-O-] x- [CO-AA1-C0-0-AD-0] y- Where O-D1-O represents a diolvolatile functionality, wherein C0-AA1-C0 is a residue of an aliphatic dicarboxylic acid functionality (preferably short chain, for example of 6 or less carbon atoms), and O-AD-O represents a residual of a symmetric crystallized diol amide preferably short chain (e.g., preferably of 6 or less carbon atoms in the diamine), where χ and y are the numbers of each repeating unit selected such that the numerical average molecular weight of the polymer is less than 2,000 g / mol. Note that while for convenience repeating units are as shown above, the polymer is not necessarily an AB block polymer.

In fact the polymer will preferably have segments with an average of 2 repeating units of the same type per segment. The order of addition and the addition time of the monomers will influence the blockiness of the structure.

The method in this case comprises providing the above polymer with a non-volatile diol having the formula H0-D2-0H to form a mixture wherein at each occurrence D2 is independently an aliphatic or heteroaliphatic, alicyclic or heteroalicyclic or aromatic or heteroaromatic group, preferably D2 is an aliphatic group, at a temperature such that the nonvolatile polymer and diol react to form a polymer having repeating units - [Hl-AA] -, - [DV-AA] -, and - [D2-0-AA] -. The temperature during the reaction is sufficiently high that at least some DV groups will be distilled during the reaction and replaced with D2-0- groups.

Thus, according to one representation the transformed polymer having the formula

H0-D2-0- [-CO-AA1-CO-O-D1, 2-0-] x- [CO-AA1-C0-0-AD-0] y-H

wherein 0-D2-0 represents residual nonvolatile diol functionality, where C0-AA1-C0 represents the oresidual of aliphatic dicarboxylic acid functionality, where 0-D1, 2-0 represents residual volatile diol functionality or nonvolatile diol functionality, where χ and y are the numbers of each of the repeating units in the polymer. Note that while convenience repeating units are as shown above, the polymer is not necessarily an AB block polymer. In fact the polymer will preferably have segments with an average of 2 repeating units of the same type per segment. The order of addition and the time of addition of monomers will influence the blockiness of the structure. The number average molecular weight of the transformed polymer being greater than 4,000 g / mol.

In the second embodiment, when the first repeating unit comprises residual of a bis amide diol, the first repeating unit may be represented by the structure - [Hl-AA] - discussed above and the second repeating unit will have the structure - [RO-AA] - where R is as defined above. Thus, according to one embodiment the polymer may have the formula HO-D1-O- [-CO-AA1-CO-ODO-] x- [Î ”AA1-C0-0-AD-0] y-Hna where ODO represents the C0-AA1-C0 represents the residual of a preferably short aliphatic dicarboxylic acid functionality, O-AD-O represents the residual of a preferably short symmetrical diol amide functionality, χ and y are the number of each of the repeating units in the polymer. Note that while for convenience repeating units are as shown above, the polymer is not necessarily an AB block copolymer. In fact the polymer will preferably have segments with an average of 2 repeating units of the same type per segment. The order of addition and the addition time of the monomers will influence the blockiness of the structure. The numerical average molecular weight of the transformed polymer being less than 2,000 g / mol. The method of this second embodiment comprises contacting the common polyol polymer having the formula M- (OH) n or a polyacid or polyacid ester having the formula M- (COOR1) n to form a mixture in which M is an n-valent organic moiety, preferably a aliphatic or heteroaliphatic, alicyclic or heteroalicyclic or aromatic or heteroaromatic group, preferably having up to 20 carbon atoms, R1 is hydrogen or an aliphatic group of 1-10 carbon atoms and where η is 3 or more, the mixture temperature being high enough to produce a material transformed having a structured structure and a numerical average molecular weight greater than 4000.

Preferably, when the polymer reacts with the polyol, the transformed material will comprise the following repeating units: - [HI-AA] -, - [R-O-AA] -, and -M- (AA) n-. Thus, according to one representation (with a single parcelapolifunctional M built into the chain, although a plurality of Μ may be possible) the transformed polymer may have the formula HO-Dl-O - [-CO-AAl-CO-O-Dl-O- ] x- [CO-AA1-C0-0-AD-0] y-CO-OM- (O- [CO-AA1-C0-0-D1] x-0- [CO-AA1-C0-0-AD -0] yH) ni, where O-D1-O represents the residual of diol functionality, C0-AA1-C0 represents the residual of aliphatic dicarboxylic acid functionality, O-AD-O represents the residual of polyamide diol functionality, χe and y are the number of each of the polymer repeat units, the numerical average molecular weight of the transformed polymer being greater than 4,000 g / mol.

Preferably, when the polymer is contacted with polyacid ester the transformed material will comprise the following repeating units: - [Hl-AA] -, - [R-O-AA] -e -M- (CO-O-R) n-. Thus, according to a representation (with a single polyfunctional portion M constructed in the chain, although a plurality of Μ is possible) the transformed polymer may have the formula HO-Dl-O - [- C0-AAl-CO-O-Dl-O -] x- [C0-AA1-C0-0-AD-0] y-C0-M- (C0-0-D1- [0-0C-AA1-C0-0-D1 -0] x- [CO- AA1-CO-O-AD-0] yH) η-χ, where O-Dl-O represents the residual of diol functionality, CO-AA1-CO represents the residual of aliphatic acid dicarboxylic functionality, O-AD-O represents the residual of functionality. polyamide diol, χ and y are the number of each of the repeating units in the polymer, the numerical average weight of the transformed polymer being greater than 4,000 g / mol. Note that while for convenience repeating units are as shown above, the polymer is not necessarily a block copolymer. In fact the polymer will preferably have segments with an average of 2 repeating units of the same type per segment. The order of addition and the addition time of the monomers will influence the blockiness of the structure.

In the first embodiment, when the first repeating unit comprises residual of a bis diamide diol and the polymer comprises residual of a volatile dicarboxylic aliphatic acid, the first repeating unit may be represented by the structure: - [Hl-AS] -, where Hl is -R- CO-NH-R-NH-CO-RO- or -R-NH-CO-R-CO-NH-RO- where any occurrence R is independently an aliphatic or heteroaliphatic, alicyclic or heteroalicyclic oraromatic or heteroaromatic group, preferably having up to 20 atoms preferably R is an aliphatic group of 1 to 10, preferably 1-4 carbon atoms and AS is -CO-R '-C0-0- where R' is an aliphatic short group, preferably 1-4 carbon atoms. carbon. The second repeating unit can be represented by the formula - [D-AS] -, where D is - [R-O] - and R is an aliphatic or heteroaliphatic, alicyclic or heteroalicyclic or aromatic or heteroaromatic group. The molecular weight of the polymer is less than 2000 g / mol. This stepolymer reacts with a high boiling point or high molecular weight diacid diacid or ester represented by the formula RO0C-HA-C00R 'where HA is an aliphatic or heteroaliphatic, alicyclic or heteroaricyclic or heteroaromatic group of 5 or more decarbon atoms. may be H or a monovalent organic group.

The reaction temperature is sufficiently high to produce a polymer having an average numerical molecular weight of 4,000 g / mol or more and comprising the following repeating units - [Hl-AS] -, - [D-AS] -, one or both of - [H1-00C-HA-C00] - and - [D-00C-HA-C00] -.

Thus, according to one representation the polymer may be represented by the formula

HO-D1-O - [- CO-AA1-CO-O-D1-O-] x- [CO-AA1-C0-0-AD-0-] y-H

where O-Dl-O represents a residual of a thiol functionality, CO-AA1-Co represents a residual of a short aliphatic dicarboxylic acid functionality, O-AD-O represents the residual of symmetric crystallized polyamythiol functionality, χ and y are the number of each of repeating units in the polymer, the numerical average molecular weight of the transformed polymer is less than 2,000 g / mol, and the high boiling diacid ester is represented by the formula R0-C0-AA2-C0-0R.

The polymer and the high boiling diacid ester combine to form a mixture and are heated to form a transformed polymer having the formula

HO-D1-O- [-C0-AA1,2-C0-0-D1-0-] x- [C0-AA1,2-C0-0-AD-0-] y-H

where C0-AA1,2-C0 represents the residual of the aliphatic dicarboxylic acid functionality or the high boiling diacid ester functionality, O-AD-O represents the residual of the polyamide diol functionality, χ and y are the number of each repeating unit in the polymer, the average molecular weight of the transformed polymer being greater than 4,000g / mol. Note that while for convenience the repeating units are as shown above, the polymer is not necessarily a block copolymer. In fact the polymer will preferably have segments with an average of 2 repeating units of the same type per segment. Addition order and monomer addition time will influence the blockiness of the structure. In another embodiment, the present invention is a polymer formed by the above branching reactions. Thus, the invention is a polymer having an average numerical molecular weight greater than 4000 g / mol and comprising the following repeating units: - [Hl-AA] -, - [RO-AA] -, and OU -M- (AA) n- OR -M- (CO-OR) n-. As a representation (with a single polyfunctional portion M constructed in the chain, although a plurality of Μ is possible), the polymer may have the formula H0-D1-0 - [- C0-AA1-C0-0-D1-0-] x- [C0-AA1 -CO-O-AD-O-] y-CO-AA1-C0-0-M- (0- [C0-AA1-C0-0-D1] x-0- [C0-AA1-C0 -0-AD-0] yH) ni, in which CO-D1-O represents the residual of diol functionality, C0-AA1-C0 represents the residual of a dicarboxylic aliphatic acid functionality, O-AD-O represents the residual of a symmetric crystallized polyamioliol In short, M is as defined above, η is 3 or more, and χ and y are the number of each of the repeating units in the polymer and the number average molecular weight is 4,000 g / mol or more. As another embodiment (with a single polyfunctional portion M-constructed in the chain, although a plurality of Μ is possible), the polymer may have the formula H0-D1-0 - [- CO-AA1-CO-O-Dl-O -] x- [C0-AA1-C0-0-AD-0-] y-C0-M- (C0-0-D1- [0-OC-AA1 -C0-0-D1 -0] x- [CO-AA1 -CO -O-AD-0] yH) η-ι, where M as defined above, η is 3 or more, O-Dl-O represents the residual of the diol functionality, CO-AA1-CO represents the residual of an aliphatic dicarboxylic acid functionality O-AD-O represents the residual of a short symmetric crystallized diol polyamide, χ and y are the number of each of the nopolymer repeat units, the number average molecular weight being greater than 4,000 g / mol. Note that while for convenience the repeating units are as shown above, the polymer is not necessarily a block copolymer. In fact the polymer will preferably have segments with an average of 2 repeating units of the same type per segment. Addition order and monomer addition time will influence the blockiness of the structure.

According to the first embodiment, when the first repeat unit comprises residual diester diamide, and the polymer comprises residual diolvolatile, the first repeat unit may be represented by the structure: - [H2-D] -, where H2 is - CO-R-CO-NH-R-NH-CO-R-CO-O- where at each occurrence R is independently an aliphatic or heteroaliphatic, alicyclic or heteroalicyclic or aromatic or heteroaromatic group, preferably R is an aliphatic group of 1 to 10, preferably of 2-4 carbon atoms and D is [ro] - and R is an aliphatic or heteroaliphatic, alicyclic or heteroalicyclic or aromatic or heteroaromatic group. The second repeating unit may be represented by the formula - [D-AA] -, where AA is -CO-R'-CO-0- where r 'is an aliphatic group, preferably from 1 to 10, preferably from 1-4 atoms. of carbon. At least one of D and preferably D in the second repeating unit is an aliphatic or heteroaliphatic, alicyclic or heteroalicyclic or aromatic or heteroaromatic group selected such that Rw (OH) 2 can be distilled from the reaction mixture. Preferably R "is an aliphatic group of 1 to 8, preferably 1 to 4 carbon atoms. The molecular weight of the polymer is less than 2,000g / mol.

Thus, according to one embodiment the polymer may have the formula HO-D1-O - [- C0-AA1-C0-0-D1-0-] x- [0-D1-0-C0-DD-CO] y- OH, where O-D1-O represents residual of a volatile diol functionality, C0-AA1-C0 represents a residual of aliphatic dicarboxylic acid functionality, O-CO-DD-CO-O represents residual of short symmetric crystallized diacidide, χ, and y is the number of each of the polymer repeat units, the number average molecular weight being less than 2,000 g / mol.

In this case, the method comprises providing the above polymer with a nonvolatile diol having the formula H0-D2-0H to form a mixture at a temperature such that the polymer and nonvolatile diol react to form a 4000 g / mol numerical average molecular weight tendon polymer. or more repeating units - [H2-D] -, - [H2-0-D2] -, - [D-AA] - (preferably - [DV-AA] -), and - [D2-O-AA ] -. During aeration, the temperature is sufficiently high that at least some DV groups will be distilled during aeration and replaced with -D2-0- groups. Thus, according to one embodiment the transformed polymer can be represented by the formula H0-D2-O - [-CO-AA1-CO-O-D1, 2-0-] x- [0-D1,2-0-C0-DD -C0] y-OH, where 0-D2-0 represents the residual of non-volatile diol functionality, CO-AA1-CO0 represents the residual of aliphatic acid dicarboxylic acid functionality, O-CO-DD-CO-O represents the residual of diacid diamid functionality, 0-D1, 2-0 represents the residual of volatile diol functionality or nonvolatile diol functionality, χ and y are the number of one of the repeating units in the polymer, the numerical average weight of the transformed polymer being greater than 4,000 g / mol. Note that while for convenience repeating units are as shown above, the polymer is not necessarily a block copolymer. In fact the polymer will preferably have segments with an average of 2 repeating units of the same type per segment. The order of addition and the addition time of the monomers will influence the blockiness of the structure.

In the second embodiment, when the first repeating unit comprises residual diester bis amide, the first repeating unit may be represented by the structure - [H2-D] - discussed above and the second repeating unit will have the structure - [RO-AA] - where R is as discussed above. Thus, according to one embodiment the polymer may be represented by the formula HO-D1-O- [-C0-AA1-C0-0-D1-0-] x- [0-D1-0-C0-DD-C0] y- OH, where O-D1-O represents residual of a volatile diol functionality, C0-AA1-C0 represents a residual of aliphatic dicarboxylic acid functionality, O-CO-DD-CO-O represents residual of short symmetric crystallized diacidide, χ, and y is the number of each of the polymer repeat units. The number average molecular weight being less than 2,000 g / mol. Note that while for convenience the repeating units are as shown above, the polymer is not necessarily an AB block copolymer. In fact the polymer will preferably have segments with an average of 2 repeating units of the same type per segment. The order of addition and the addition time of the monomers will influence the blockiness of the structure.

The method of this second embodiment comprises contacting the opolymer with a polyol having the formula M- (OH) n or a polyacid ester having the formula M- (COOR1) n to form a mixture in which M is an n-valent organic moiety, preferably a group. aliphatic or heteroaliphatic, alicyclic or heteroalicyclic or aromatic or heteroaromatic, preferably having up to 20 carbon atoms, R1 is hydrogen or an aliphatic group of 1-10 carbon atoms and η is 3 or more, the mixture temperature being sufficiently high to produce a transformed material having a branched structure of a numerical average molecular weight greater than 4000.

Preferably, when the polymer reacts with the polyol, the transformed material will comprise the following repeating units: - [H2-D] -, - [R-O-AA] -, and -M- (AA) n-. According to one embodiment this transformed polymer may be represented by the formula (with a single multifunctional parcel M built into the chain, although a plurality of M may be possible): HO-Dl-O - [- CO-AAl-C0-0-D1-0-] x- [O-D1-O-CO-DD-CO-] y-0-M- (0- [-C0-AA1-C0-0-D1] x- [0-D1-0-C0-DD- C0] y-0H) n_i, where O-D1-O represents residual diol functionality, C0-AA1-C0 represents residual aliphatic dicarboxylic acid functionality, 0-C0-DD-C0-0 represents diacid diacid functionality residual, χ and y are the number of each of the repeating units in the polymer.

Preferably, when the polymer contacts the depolyacid ester the transformed material will comprise the following repeating units: - [H2-AA] -, - [RO-AA] -, and M- (COOR) n-- According to one embodiment ( with a single polyfunctional portion M constructed in the chain, although a plurality of Μ is possible) the transformed polymer can be represented by the formula: HO-Dl-Ο - [- CO-AAl-CO-O-Dl-O-] x- [OC -DD-CO-D1-O] y-OC-M- ([-C0-0-D1-0-CO-AA1-C0-] X- [0-D1-0-C0-DD-C0] y- 0H) n_i, where O-Dl-O represents diol functionality residual, CO-AA1-CO represents aliphatic dicarboxylic acid functionality residual, O-CO-DD-CO-O represents residual diacid diacid defunctionality, χ and y are the number of one of the repeating units in the polymer. Note that while for convenience the repeating units are as shown above, the polymer is not necessarily a strict block copolymer. In fact the polymer will preferably have segments with an average of 2 repeating units of the same type per segment. The order of addition and the addition time of the monomers will influence the blockiness of the structure.

In the first embodiment when the first repeating unit comprises residual diamide diester and the polymer comprises residual aliphatic dicarboxylic acid, the first repeating unit may be represented by the structure: - [H2-D] - and the second repeating unit may be represented by formula - [SA-D] - where H2 and SA are as defined above and D is - [R-0] -and R is an aliphatic or heteroaliphatic, alicyclic or heteroalicyclic or aromatic or heteroaromatic group. The number average molecular weight of the polymer is less than 2000 g / mol. This polymer reacts with a high molecular weight or high deblocking diacid or diacid ester represented by the formula RO0C-HA-C00R 'where HA is an aliphatic or heteroaliphatic, alicyclic or heteroalicyclic or aromatic or heteroaromatic group of 5 or more carbon atoms and R 'may be H or a monovalent organic group. The reaction temperature is sufficiently high to produce a polymer having a number average molecular weight of 4000 g / mol and comprising the following repeating units: - [H2-D] -, - [SA-D] -, and - [D-OOC- HA-COO] -.

Thus, according to one embodiment the polymer may be represented by the formula HO-D1-O - [- C0-AA1-C0-0-D1-0-] x- [0-D1-0-C0-DD-C0] y -0H, where O-D1-O represents a diol functionality, C0-AA1-C0 represents a diol functionality of a short di-carboxylic acid functionality, O-CO-DD-CO-O represents a residual of a symmetrical crystallized diacid diamide short, χ and y are the numbers of each of the repeating units, the number average molecular weight being less than 2,000 g / mol. According to this embodiment the polymer contacts a high boiling diacid ester having the formula RO-CO-AA2-CO0R to form a mixture, the temperature of the mixture being sufficiently high to produce a transformed material comprising a transformed polymer represented by the formula D1-O- [-C0-AA1,2-C0-0-D1-0-] x- [C0-AA1,2-C0-0-C0-DD-C0] y-OH, where C0-AA1, 2-C0 represents residual aliphatic carboxylic acid functionality or high-wasting diacid ester functionality, O-CO-DD-CO-O represents residual diacid diamide functionality, χ and y are the numbers for one of the repeating units, number average molecular weight of the transformed polymer being greater than 4,000 g / mol. Note that while for convenience the repeating units are as shown above, the polymer is not necessarily a strict block copolymer. In fact the polymer will preferably have segments with an average of 2 repeating units of the same type per segment. The order of addition and the addition time of the monomers will influence the blockiness of the structure.

In another embodiment, the present invention is a polymer formed by the above branching reactions. Thus, the invention is a polymer having an average numerical molecular weight greater than 4000 g / mol and comprising the following repeating units: - [H2-D] -, - [RO-AA] -, and -M- (AA) n- or -M- (COOR) n-- Thus, according to one embodiment the polymer can be represented by the formula (with a single polyfunctional portion M constructed in the chain, although a plurality of M is possible): HO-DI-O- [-CO- AA1-CO-O-D1-O-] x- [0-D1-0-C0-DD-C0-] y-0-M- (0- [C0-AA1-CO-0-D1] x-0 - [0-DI-0-CO-DD-CO] y-OH) ni, where 0-DL-O represents the residual of the diol functionality, CO-AA1-CO represents the residual of a short aliphatic acid dicarboxylic functionality, O -CO-DD-CO-O represents the oreside of a short symmetric crystallized diacid diamide, M is as defined above, η is 3 or more, and χ and y are the numbers of each of the nopolymer repeat units. According to another embodiment (with a single polyfunctional portion M built into the chain, although a plurality of Μ is possible) the polymer may be of the formula HO-Dl-O- [-CO-AAl-CO-O-Dl-O-] x - [0C-DD-C0-0-D1-0-] y-OC-M - ([- C0-0-D1-0-C0-AA1-C0-] x [0-D1-0-C0-DD -CO] y-OH) ni, where M is as defined above, η is 3 or more, O-D1-O represents the residual of the diol functionality, C0-AA1-C0 represents the residual of a short aliphatic dicarboxylic acid functionality, 0 -C0-DD-CO-O represents the residual of a short symmetric diacrystallized diacid, χ and y are the numbers of one of the repeating units and the number average molecular weight being greater than 4,000 g / mol.

Although US Patent No. 6,172,167 teaches a process for producing aliphatic polyester amide compositions and methods for preparing them, the process of the Ί67 patent is relatively time consuming when it is desired to produce polymers having a molecular weight of 4,000 g / mol or more. The invention provides a relatively rapid process for producing polymers having a molecular weight of 4,000 g / mol or more.

The present invention begins with a preliminary polymer discussed above. The use of short symmetric diolcrystallized amide functionality or dediamide diester functionality in the starting polymer followed by the step of increasing its molecular weight, for example by common non-volatile diol reaction, is believed to be important to produce an increased molecular weight polymer composition having superior mechanical properties and excellent phase separation.

As taught in USP 6,172,167, fully incorporated herein by reference, such prepolymer polymers may be prepared from mixtures comprising a diol amide. Diol amides which are particularly useful in the practice of the invention have the following structure:

HO- (CH2) n -CONH- (CH2) m- (X) k- (CH2) m-CONH- (CH2) n-OH where X is NH, OouS, kéOOal, medela4ené

from 4 to 6.

The diol amide may be prepared by any suitable means, however it has been found to be advantageous to prepare the diol amide by the ring opening polymerization (ROP) reaction between at least one primary diamine and at least one lactone. The preparation of amythiol may also be performed according to the methods described in US Patent No. 3,025,323 and in the Synthesis of Alternate Polyamide-Urethanes by Reacting Diisocyanates with N, N'-Di (6-Hydroxycaproyl) alkylenediamines and N-Hydroxyalkyl -6-hydroxycaproamide "by S. Katayama et al in J.Appl. Polym I know, volume 15, 775-796 (1971).

In this specification a primary diamide is defined as an organic compound comprising two primary amine groups. The primary diamine may also comprise secondary and tertiary amino groups. Suitable diamine are ethylene diamine, diethylene triamine, butane diamine and hexane diamine.

Preferably, lactone has 4, 5 or 6 carbon atoms. Suitable lactones include γ-butyrolactone, δ-valerolactone, ε-caprolactone, pentadeca-lactone, glycolides and lactides. The preferred method of carrying out the reaction is to mix in a stainless steel stirred tank reactor lactone with diamine in a ratio of at least 2 mol lactone per mol diamine, preferably in a ratio of 2.0 to 2.5 mol lactonapor. mol of diamine. Preferably, the reaction is performed under a nitrogen layer. Reagents may be dissolved in a solvent, but it is generally preferable to perform the reaction in the absence of a solvent in order to eliminate the effort required to separate the solvent from the polymeric product composition. Preferably, the reaction temperature is maintained at a value that is less than the melting point of the pure diol amide, preferably between 500 ° C and 900 ° C by controlling the heat released by the efficient cooling reaction which generally results in a product comprising a high fraction of the desired diol amine product that may be present. be used in subsequent process steps without the need for further purification. If the reaction is performed in the absence of a solvent, generally all reactor contents will solidify. It is generally advantageous to allow the reactant mixture to solidify to room temperature and to allow the reaction product to remain for several hours, preferably for more than 6 hours, more preferably for more than 12 hours to allow any remaining diamine to reign. The product amide diol can then be removed from the reactor by heating the reactor contents, preferably under an inert gas layer, until the product melts.

Alternatively the diol amide may have the following general structure

HO- (CH2) n -NH-CO- (CH2) m- (Xlk- (CH2) m -CO-NH- (CH2) n-OH prepared by reacting a dicarboxylic acid ester (e.g. diethyl oxalate [m = k = 0] or dedimethyl adipate [m = 4 and k = 0]) with a stoichiometric amount of an alkanolamine such as ethanolamine (n = 2) The reaction may be catalyzed using a catalyst such as stannous octoate, titanium (IV) tetrabutoxy or phenol.

A particularly preferred diol amide is dimer prepared from ethylenediamine and ε-caprolactone having the following structure:

HO- (CH2) 5-COH- (CH2) 2-COH- (CH2) 5-0H

The aliphatic polyester-amide polymer having a molecular weight of less than 2,000 g / mol may be prepared by containing a low molecular weight diol amide diol and a low molecular weight diol, heated to liquid the mixture after the catalyst is injected.

Low molecular weight dicarboxylic acid diesters are defined as those having a molecular weight of less than 150 g / mol. The alkyl moieties of the dicarboxylic acid diester are preferably the same or different and have from 1 to 3 carbon atoms.

Preferably, the alkyl moieties are methyl groups. The dicarboxylate acid diester ester dicarboxylate has from 2 to 8 carbon atoms, most preferably from 4 to 6 carbon atoms.

Preferably, the dicarboxylate moiety is a succinate, glutarate or adipate group. Suitable dicarboxylic acid esters include dimethyl succinate, dimethyl adipate, dimethyl oxalate, dimethyl malonate and dimethyl glutarate.

The reaction is usually performed in a stirred heated devolatilizer or reactor equipped with a reflux column under a layer of inert gas. In a preferred embodiment, the solid diol amide is first mixed with the dicarboxylic acid diester. Thereafter, the mixture of amide diol and di-dicarboxylic acid diester is heated to a temperature of about 140 ° C or to a temperature at which the diol amide dissolves completely. Thereafter, the mixture of amythiol and dicarboxylic acid diester is maintained at this temperature for 1.5 to 3 hours. To minimize the discolouration of bisamide diol first mix with dimethyl adipate at room temperature and then heat the mixture to make it liquid while at the same time believing that the very reactive free amine functions are captured by transamidation reaction with dimethyl adipate in Amide functions. Then the diol is added and finally the catalyst (at a time when it is believed that the highly aggressive species have already reacted).

The low molecular weight excess stoichiometric diol is introduced, the mixture is homogenized and finally the catalyst is formed to form the polyesteraliphatic / amide polymer having a number average molecular weight of less than 200 g / mol.

In this specification volatile diols are defined as having a molecular weight lower than 1,8-octanediol. Suitable diols include monoethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol. Volatile diol is added to the polymer and the mixture is generally homogenized by continuous stirring. Generally, the temperature is maintained at or above the melting temperature of the amide diol, typically at about 140 ° C. Preferably, the reaction is carried out under an inert gas layer at near atmospheric pressure. Then, preferably, a catalyst is added to the reaction mixture. Any suitable compound may be used to catalyze transesterification and transamidation reactions. Suitable catalysts include titanium (IV) tetrabutoxy, zinc acetate and magnesium acetate.

The addition of volatile diol and optional catalyst results in the evolution of a vapor comprising the alcohol under molecular weight or an alcoholic mixture corresponding to the alkyl moiety or moieties of the dicarboxylic acid esters. At near atmospheric pressure, the reaction mixture vapor comprising the polymer is distilled off. The reaction continues until the evolution of alcohol decreases in intensity.

In this specification, non-volatile diols having a molecular weight lower than 1,7-heptanediol are defined.

Here the short crystallized diamide diacid functionality is the same as defined and taught in USP 6,172,167 above (see, especially column 4, line 58 and column 7, line 37).

In this specification, high boiling dicarboxylic acid diesters are defined as having a molecular weight greater than 174. The alkyl portions of the dicarboxylic acid diester are preferably the same or different and have from 1 to 3 carbon atoms. Preferably, the alkylating moieties are methyl groups. Preferably, the carboxylic acid moiety has between 7 and 10 carbon atoms, most preferably or 9 or 10 carbon atoms.

Preferably the dicarboxylic acid moiety is aazelate or sebacate group or dimer acid group. Preferred dicarboxylic acid esters are dimethyl azelate, dimethyl sebacate or dimethyl suberate.

Suitable non-volatile diols in the present invention include higher glycols such as dipropylene glycol or tripropylene glycol, polyethylene glycols (molecular weight PEGs 400 to 8000 and EO capped poly (propylene glycols) molecular weight 400 to 4000), diol dimers or soya polyols or other high molecular weight natural diols such as those mentioned in Jetter et al, Phytochemistry 55, 169-176 (2000). Suitable polyols for use in the present invention include glycerol, trimethylolpropane, sorbitol and sucrose (as such also propoxylated or ethoxylated).

The reaction of the aliphatic polyester-amide polymer with the nonvolatile diol, depolyacid ester or high boiling dicarboxylic acid diester is generally carried out under an inert gas layer. The mixture is then heated for a period typically 2 to 3 hours at a temperature of about 180 ° C or at such a temperature that the amid ester polymer remains in a molten or dissolved state. Typically the pressure is close to atmospheric pressure. The reaction may result in the evolution of low molecular weight alcohol that is distilled from the system. It is then gradually lowered to an absolute pressure of about 5 millilibars to initiate vacuum distillation of any volatile materials. The resulting polymeric composition may then be cooled to about 1500 ° C and brought to atmospheric pressure, after which the polymer may be removed from the reactor while still in the molten state.

Preferably the catalysts are present in the preformed formulation and in this case there is no need to add further catalyst to allow the branching or pesomolecular enhancement reaction.

The polymers of the present invention may have mechanical properties (such as strength, stiffness, elasticity and buildability) comparable to those of polyethylene.

Conclusion

Although the present invention has been described above according to its preferred embodiments, it may be modified within the spirit and scope of this disclosure. Therefore, this patent application is intended to cover any variations, uses, or adaptations of the present invention using the general principles disclosed herein. In addition, the present patent application is intended to cover such departures from the present disclosure that arise from known and customary practice in the art to which this invention belongs and which fall within the limits of the following claims.

Examples

Preparation of the ethylene diol amide-N, N'-dihydroxyhexanamide (C2C) monomer.

A 10 L stainless steel reactor equipped with a stirrer and a caprolactone (5.707 kg, 50 moles), nitrogen-purified water reactor is charged. Immediately, add EDA (1.502 kg, 25mols) with rapid stirring. After a period of induction, a slow exothermic reaction begins. Gradually the reactor temperature rises to 900C under maximum applied cooling. A white deposit forms and the reactor contents solidify when agitation is stopped. The contents are then cooled to 20 ° C and then allowed to rest for 15 hours. The reactor contents are then heated to 140 ° C at which the solidified reactor contents fuse; and then heat to 16 ° C under continuous stirring for at least 2 hours. Then the liquid product is discharged from the reactor into a collecting tray. A nuclear magnetic resonance study of the resulting product shows that the molar concentration of C2C in the product exceeds 80 percent. The melting point is determined to be 140 ° C. The solid material is granulated and used without further purification.

A4A Diamide Diester Monomer Preparation

In a nitrogen atmosphere, detitanium (IV) butoxide (0.92 g, 2.7 mmol), ethylenediamine (15.75 g, 0.262 mol), and dimethyl adipate (453.7 g, 2.604 mol) are charged to a flask. 1 L round neck with 3 necks which is capped and transferred to a hood. The positive nitrogen flask is placed via a fixed inlet adapter on a Firestone valve. A blade agitator shaft is inserted into the flask together with a stirring pad with an upper stirring motor. A capped condenser is inserted into the flask. A partermoelectric is also inserted through septa. The balloon is heated with a hemisphere thermal blanket which is attached to a proportional temperature controller. The basic reaction profile is 2.0 hours / at 50 ° C; 2.0 hours / at 60 ° C; 2.0 hours / at 80 ° C; overnight at 100 ° C. Stir the flask with stirring at ~ 50 ° C, stop stirring and cool to room temperature. Approximately 200 mL of stirring cyclohexane is added to a solid filterable slurry collected in a filtration funnel. glass of medium composition. The collected solids are washed twice with -50 mL cyclohexane. The product is dried overnight in a vacuum oven at -50 ° C. The dried product is broken down and re-slurried in fresh cyclohexane (-300 mL), collected by filtration, rinsed twice with -50 mL cyclohexane and dried to constant weight in a vacuum oven at 50 ° C under vacuum. full pump Yield = 59.8 g (66%).

Preparation of prepolymers

Example A. Preparation of C2C prepolymer, dimethyl adipate, and 1,4-butanediol.

In an inert atmosphere a 250mL round bottom flask is charged with titanium (IV) butoxide (0.194 g, 0.571 mmol), N, N'-1,2-ethanediyl-bis [6-hydroxyhexanamide] (13.62 g, 47.22 mmol), dimethyl adipate (65.80 g, 0.3777 mol), and 1,4-butanediol (59.57 g, 0.6611 mol). Polymerization sandblasting occurs with aerial agitation, nitrogen / vacuum, heating, and use of a distillation head. The reaction profile is as follows: 2.0 h at 160 ° C to 175 ° C, N2; 5 minutes, 450 Torr; 10 minutes, 50Torr; 5 minutes, 40 Torr; 10 minutes, 30 Torr; 10 minutes, 20 Torr; 10 minutes, 15 Torr; 90 minutes, 10Torr; 1.0 h, 0.425 to 0.60 Torr. After cooling a waxy solid has Tm = 51 ° C (55 J / g); inherent viscosity = 0.090 dL / g (chloroform / methanol (1/1, w / w), 30.0 ° C, 0.5 dL / g); Mn via 1H NMR -1098; and -12 mol% C 2 C incorporation via 1H NMR.

Example B. Preparation of A4A prepolymer, dimethyl adipate, and 1,4-butanediol.

In an inert atmosphere a 250mL round bottom flask is charged with titanium (IV) butoxide (0.174g, 0.512mmol), 7,12-diaza-6,13-dioxo-1,18-octadecanedioatode dimethyl (31.68g , 85.06 mmol), dimethyl adipate (44.45 g, 0.2552 mol), and 1,4-butanediol (61.33 g, 0.6805 mol). The polymerization reaction occurs with air agitation, nitrogen / vacuum, heating, and the use of a distillation head. The reaction profile is as follows: 2.0 hr from 160 ° C to 175 ° C, N2; 5 minutes, 450 Torr; 5 minutes, 100Torr; 10 minutes, 50 Torr; 5 minutes, 40 Torr; 10min, 30 Torr; 10 minutes, 20 Torr; 10 minutes, 15Torr; 90 minutes, 10 Torr; 1.0 h, -0.400 Torr. After cooling a waxy solid has bimodal Tm = 47 and 95 ° C, inherent viscosity = 0.091 dL / g (chloroform / methanol (1/1, w / w), 30.0 ° C, 0.5 dL / g); Mn via 1H NMR -1049; e-24 mole% incorporation of A4A via 1H NMR. Preparation of polymers

Example 1. Reaction of C2C prepolymer, dimethyl adipate, and 1,4-butanediol with polytetrahydrofuran.

In an inert atmosphere, a 250mL round bottom flask is charged with titanium (IV) butoxide (0.091 g, 0.27 mmol), prepolymer of Example A (40.00 g), epolytetrahydrofuran (10.00 g, 10 mL). , 17 mmol, Mn 983, TERATHANE ™ 1000). The polymerization reaction occurs with aerial comagitation, nitrogen / vacuum, heating, and the use of a distillation head. The reaction profile is as follows: 1.0 hr from 160 ° C to 175 ° C, N2; 1 h, 0.3 to 0.6Torr, 175 ° C; and 6 h, -0.30 Torr, 190 ° C. After cooling a hard solid has Tm = 57 ° C (28 J / g); inherent viscosity = 0.60 dL / g (chloroform / methanol (1/1, w / w), 30.0 ° C, 0.5 dL / g); Mn via 1H-16000 NMR.

Example 2. Reaction of C2C prepolymer, dimethyl adipate, and 1,4-butanediol with glycerol ethoxylate.

In an inert atmosphere, a 25 µmL round bottom flask is charged with antimony oxide (0.0128 g, 0.04 39 mmol), calcium acetate monohydrate (0.0494 g, 0.280 mmol), prepolymer of Example A ( 44.00 g), and glycerol ethoxylate (2.00 g, 2.00 mmol, Mn 999). The polymerization reaction occurs with air agitation, nitrogen / vacuum, heating, and the use of a distillation head. The reaction profile is as follows: -1.8 h from 160 ° C to 175 ° C; 0.2 to 0.9 Torr. After cooling a hard solid has Tm = 66 ° C (40 J / g); inherent viscosity = 0.27 dL / g (chloroform / methanol (1/1, w / w), 30.0 ° C, 0.5 dL / g).

Example 3. Reaction of A4A prepolymer, dimethyl adipate, and 1,4-butanediol with dimethyl sebacate. A 25 µm round bottom flask with antimony oxide (0.0128 g, 0.0439 mmol) is charged, calcium acetate hydrochloride (0.0494 g, 0.280 mmol), prepolymer of the

Example B (44.00 g), and dimethyl sebate (2.41 g, 10.5 mmol). The polymerization reaction occurs with air agitation, nitrogen / vacuum, heating, and the use of a distillation head. The reaction profile is as follows: 2 h from 160 ° C to 175 ° C, N2; 5 minutes, 450 Torr; 5 minutes, 100Torr; 10 minutes, 50 Torr; 5 minutes, 40 Torr; 15 minutes, 30 Torr; 15 minutes, 20 Torr; 90 minutes, 10Torr; 2 h, 0.4-0.6 Torr, 175 ° C; 2.5 h, 0.3-0.4 Torr at 190 ° C. After cooling a hard solid has bimodal Tm = 69 and 114 ° C (43 J / g); inherent viscosity = 0.28 dL / g (chloroform / methanol (1/1, w / w), 30.0 ° C, 0.5 dL / g); NMR NMR 1H -7000.

Example 4. Reaction of A4A prepolymer, dimethyl adipate, and 1,4-butanediol with trimethyl 1,3,5-benzene tricarboxylate.

A 25 OmL round bottom flask is charged with antimony oxide (0.0128 g, 0.0439 mmol), calcium acetate hydrochloride (0.0494 g, 0.280 mmol), Example B prepolymer (44.00 g ), and 1,3,5-benzene tricarboxylate detrimethyl (0.529 g, 2.10 mmol). The polymerization reaction occurs with air agitation, nitrogen / vacuum, heating, and the use of a distillation head. The reaction profile is as follows: 2.3 h at 160 ° C to 175 ° C, N2; 5 minutes, 100 Torr; 10 minutes, 50Torr; 5 minutes, 40 Torr; 15 minutes, 30 Torr; 15 minutes, 20 Torr; 90 minutes, 10 Torr; -2.5 h, 0.2-0.6Torr. After cooling a hard solid has bimodal Tm = 73e100 (44 J / g); inherent viscosity = 0.29 dL / g (chloroform / methanol (1/1, w / w), 30.0 ° C, 0.5 dL / g). Comparative example 1. C4C and 1,4-butanediol reaction dimethyl comadipate; 25 mole% polyester amide C4C deunits (according to Stapert et al., US 6,172,167, Example 4).

Dimethyl adipate (70 g, 0.402 mol), C4 C (31.79 g, 0.101 mol) and twice excess 1,4-butanediol (54.07 g, 0.602 mol) were weighed into a reaction vessel which was placed in a nitrogen atmosphere. Ti (OBu) 4 catalyst was added in an amount of 0.1% by weight based on the total mixture. Methanol was distilled off at 175 ° C for 2 hours. A low vacuum (p => 5 mbar) was then applied for 1h after which time the temperature was raised to 185-190 ° C. At this temperature a vacuum (p = 0.1 bar) was applied to remove excess 1,4-butanediol for 15-20 h. The molten material was cooled to crystallize the product.

Comparative Example 2. Reaction of A4A and dimethyl adipate with 1,4-butanediol; 25 mole% polyester amide from A4A units (according to Stapert et al., US 6,172,167, Example 5).

A reaction vessel was charged with 14.6 g (0.084 mol) of dimethyl adipate, 30.1 g (0.333 mol) 1,4-butanediol and 31.1 g (0.084 mol) A4A, which was placed. in a nitrogen atmosphere. Mixture of Ti (OBu) 4 catalyst was added at a concentration of 0.1% by weight. Methanol was distilled at 1750 ° C for 2 hours. A low vacuum was then applied for 1h. The temperature was raised to 185-190 ° C and full vacuum (p = 0.1 mbar) was applied for 5-10 hours to remove excess 1,4-butanediol.

Amide-ester polymer composition characteristics The physical properties of the above-obtained amide-ether polymers are summarized in Table 1 below. Numerical average molecular weights are determined by 1H nuclear magnetic resonance using a Bruker Avance 300 NMR spectrometer with a 5 mm probe head. The melting points of the samples are determined by differential scanning calorimetry using a PerkinElmer obtainable Pyris 1 apparatus.

Mechanical tests are performed on samples prepared from compression molded plates. Prior to compression demoulding the samples are dried at 600 ° C for about 24 hours. The plates are prepared in a Passassena SQL-4300 press, the samples being compression molded at 1600C in 30 tons for about 2 minutes. After compression molding, the samples are cooled-tempered to room temperature. The plates thus obtained are 70 millimeters wide, 100 millimeters long and 2 millimeters thick.

Table 1. Physical and mechanical properties of amide ester polymers

<table> table see original document page 28 </column> </row> <table>

Claims (45)

Method for increasing the molecular weight of a polymer, characterized in that it comprises the steps of: (A) providing a reactant mixture including (I) an initial polymer having a molecular weight of less than 2000g / mol, said polymer comprising a first unit of A repeat, which comprises the residue of a condensation reaction or an aliphatic dicarboxylic acid with a bis amide diol or a diol with a dediamide diester, and a second repeat unit comprising the residue of a condensation reaction of a thiol with a dicarboxylic acid aliphatic as long as at least one of the aliphatic diol or dicarboxylic acid is distinguished by the fact that when independently found in a reagent mixture they are relatively volatile and may be removed by distillation of the reagent mixture and (II) a selected reagent of nonvolatile diols and nonvolatile aliphatic dicarboxylic acids; and (B) heating the reagent mixture to increase the polymer molecular weight to 4000g / mol or more. Method according to Claim 1, characterized in that the starting polymer comprises the residual of a bis amide diol and the residual of a volatile and oreagent diol is a non-volatile diol. Method according to claim 2, characterized in that the starting polymer comprises a first repeating unit represented by the structure: - [H1-AA] -, where H1 is -R-CO-NH-R-NH-CO- RO- or -R-NH-CO-R-CO-NH-RO-, where at each occurrence R is independently an aliphatic or heteroaliphatic, alicyclic or heteroalicyclic or aromatic or heteroaromatic group and AA is -CO-R'-CO-O- where R 'is an aliphatic group and a second repeating unit represented by the formula - [DV-AA] - where DV is - [R "-0] - and R" is a selected aliphatic or heteroalicyclic or heteroaromatic or heteroalicyclic aliphatic group such that R '(OH) 2 may be removed from the reaction mixture by distillation. Method according to claim 2, characterized in that the starting polymer has the formula HO-D1-O - [-CO-AA1-C0-0-D1-0-] x- [C0-AA1-C0- 0-AD] y-0H, where O-Dl-O represents a volatile diol functionality, C0-AA1-C0 represents a short dicarboxylic aliphatic acid functionality, O-AD-O represents a short symmetric crystallized diol functionality, χ and y are the numbers of each of the polymer repeat units, the number average molecular weight being less than -2,000 g / mol, comprises the step of: contacting the polymer with a nonvolatile diol having the formula H0-D2-0H to form a mixture, the temperature of the mixture be sufficiently high to produce a transformed material comprising a transformed polymer having the formula H0-D2-0- [-C0-AA1-C0-0-D1,2-0-] x- [C0-AA1-C0-0-AD] y- 0H, where 0-D2-0 represents the volatile diolon functionality, C0-AA1-C0 represents the aliphatic acid dicarboxylic acid functionality, O-AD-O represents the function polyamide diol, 0-D1, 2-0 represents volatile diol functionality or nonvolatile diol functionality, χ and y are the numbers of each of the repeating units in the polymer, the number average molecular weight of the transformed polymer being greater than 4,000 g / mol. Method according to claim 1, characterized in that the starting polymer comprises the residual of a bis amide diol and the residual of a volatile dicarboxylic aliphatic acid and the reagent is a nonvolatile dicarboxylic aliphatic acid. Method according to claim 5, characterized in that the starting polymer comprises a first repeating unit represented by the structure: - [H1-SA] -, where H1 is -R-CO-NH-R-NH-CO-1. R-0- or -R-NH-CO-R-CO-NH-RO- where at each occurrence R is independently an aliphatic or heteroaliphatic, alicyclic or heteroalicyclic or aromatic or heteroaromatic group, and SA is -CO-R'-CO- O- where R 'is a short aliphatic group, D is - [R-Ο] - and R is an aliphatic or heteroaliphatic, alicyclic or heteroalicyclic or aromatic or heteroaromatic group. Method according to claim 5, characterized in that the starting polymer has the formula HO-D1-O - [- CO-AA1-CO-O-D1-O-] x- [CO-AA1-CO- O-AD] y-0H, where O-Dl-O represents a diol functionality, C0-AA1-C0 represents a short aliphatic dicarboxylic acid functionality, O-AD-O represents a short symmetric diolcrystallized polyamide functionality, χ and y are the numbers After one of the repeating units in the polymer, the numerical average weight of the polymer being less than 2,000 g / mol comprises the step of: contacting the polymer with a high boiling diacid ester having the formula RO-CO-AA2-C0- 0R to form a mixture, until the temperature of the mixture is high enough to produce a transformed material comprising a transformed polymer having the formula H0-D1-0 - [-CO-AA1,2 -CO-O-Dl-O-Jx- [C0-AAl , 2-CO-0-AD] y-OH, wherein CO-AA1,2-CO represents aliphatic dicarboxylic acid functionality or diacyl ester functionality. high-melting point acid, O-AD-O represents the polyamidiol functionality, χ and y are the numbers of each of the repeating units in the polymer, the number average molecular weight of the transformed polymer being greater than 4,000 g / mol. Method according to claim 1, characterized in that the starting polymer comprises the residual of a diamide diester and the residual of a volatile diol and the reagent is a non-volatile diol. A method according to claim 8, characterized in that the starting polymer comprises a first repeating unit represented by the structure: - [H2-D] -, where H2 is -C0-R-CO-NH-R-NH- C0-R-C0-0-, where at each occurrence R is independently an aliphatic or heteroaliphatic, alicyclic or heteroalicyclic or aromatic or heteroaromatic group and a second repeating unit represented by the formula - [D-AA] -, where AA is -CO-Ri- Where R 'is an aliphatic group, provided that Dem at least one of the first and second repeating units is a volatile diol. Method according to claim 8, characterized in that the starting polymer has the formula HO-D1-O- [-C0-AA1-C0-0-D1-0-] x- [0-D1-0- C0-DD-C0-0-0] yH, where O-D1-O represents a diolvolatile functionality, C0-AA1-C0 represents a short aliphatic acid dicarboxylic acid functionality, O-CO-DD-CO-O represents a crystallized diacid diamid functionality, symmetric short, χ and y are the numbers of each of the repeating units in the polymer, the average molecular weight of the polymer being less than 2,000 g / mol, understanding the step of: contacting the polymer with a volatile diolon having the formula H0-D2- 0H to form a mixture, the temperature of the mixture being sufficiently high to produce a transformed material comprising a transformed polymer having the formula H0-D2-0- [-C0-AA1-C0-0-D1,2-0-] x- [0-D1 , 2-0-CO-DD-C0] y-OH, where 0-D2-0 represents nonvolatile diol functionality, C0-AA1-C0 represents aliphatic acid dicarboxylic acid functionality o, O-CO-DD-CO-O represents diacid diamid functionality, 0-Dl, 2-0 represents volatile diol functionality or nonvolatile diol functionality, χ and y are the numbers of each of the repeating units in the polymer, the molecular weight numerical mean transformed polymer being greater than 4,000 g / mol. Method according to claim 1, characterized in that the starting polymer comprises the residual of a diester bis amide and the residual of a volatile dicarboxylic acid and the reagent is a nonvolatile carboxylic acid. Method according to claim 11, characterized in that the starting polymer comprises a first repeating unit represented by the structure: - [H2-D] - and a second repeating unit represented by the formula - [SA-D] -, wherein H2 is -C0-R-CO-NH-R-NH-CO-R-CO-O-, where at each occurrence R is independently an aliphatic or heteroaliphatic, alicyclic or heteroalicyclic or aromatic or heteroaromatic group, SA is -CO-R ' -CO-O- where R 'is a short aliphatic group, and where D is - [RO] -. Method according to claim 11, characterized in that the starting polymer has the formula HO-D1-O - [- C0-AA1-C0-0-D1-0-] x- [0-D1-0- C0-DD-C0] y-OH, where O-D1-O represents a diol functionality, C0-AA1-C0 represents a short aliphatic acid dicarboxylic acid functionality, O-CO-DD-CO-O represents a symmetric crystallized diacid diamide functionality In short, χ and y are the numbers of each repeating unit in the polymer, the average molecular weight of the polymer being less than 2,000 g / mol, comprising the step of: contacting the polymer with a diacid ester having the formula RO-CO-AA2 -C0-0R to form a mixture, the temperature of the mixture is sufficiently elevated to produce a transformed material comprising a transformed polymer having the formula HO-D1-O- [-C0-AA1,2-C0-0-D1-0-] x- [ C0-AA1,2-C0-0-C0-DD-C0] y-OH, where C0-AA1,2-C0 represents aliphatic dicarboxylic acid functionality or high-point diacid ester ester functionality In the melt range, O-CO-DD-CO-O represents diacid diacid functionality, χ and y are the numbers of each of the repeating units in the polymer, the number average molecular weight of the transformed polymer being greater than 4,000 g / mol. A method for increasing molecular weight and polymerization in a polymer comprising (A) providing a reactant mixture including (I) an initial polymer having a molecular weight of less than 2000g / mol, said polymer comprising a first repeat unit, which comprises the residue of a condensation reaction or an aliphatic dicarboxylic acid with a bis amide diol or a diol with a dediamide diester, and a second repeating unit which is the same as a condensation reaction of a diol with a dicarboxylic acid aliphatic and (II) a selected polyol and polyacid reagent or an ester of such polyol acids, wherein the reagent has at least three functional groups -OH, -ester, or -COOH where appropriate (B) heat the reactant mixture to form a polymerized polymer having a molecular weight of at least 4000g / mol. Method according to claim 14, characterized in that the starting polymer comprises the residual of a bis amide diol and the reagent is a polyol. Method according to claim 15, characterized in that the starting polymer comprises a first repeating unit represented by the structure - [H1-AA] -, where H1 is -R-CO-NH-R-NH-CO-RO -or-R-NH-CO-R-CO-NH-RO- where at each occurrence R is independently an aliphatic or heteroaliphatic, alicyclic or heteroalicyclic or aromatic or heteroaromatic group and AA is -C0-R'-C0-0- where R 'is an aliphatic group and a second repeating unit having the structure - [R-0-AA] - where R is as defined above and opoliol is represented by the formula M (OH) n, where M is an n-valiant organic moiety and η is an integer of 3 or more. Method according to claim 16, characterized in that the branched polymer comprises the following repeating units: - [Hl-AA] -, - [R-O-AA] -, and -M- (AA) n-. Method according to claim 16, characterized in that the starting polymer has the formula H0-D1-0- [-C0-AA1-C0-0-D1-0-] x- [C0-AA1-C0- 0-AD - 0] y - H, where O-D1-O represents a diol functionality, C0-AA1-C0 represents a short aliphatic acid dicarboxylic acid functionality, O-AD-O represents a crystallized, symmetrical diol polyamide functionality, χ and y are the numbers of each of the repeating units in the polymer, the number average molecular weight of the polymer being less than 2,000 g / mol, understanding the step: contacting the polymer with a polyol having the formula M- (OH) n to form a mixture, wherein η is 3 or more, the temperature of the mixture being sufficiently high to produce a transformed material comprising a transformed polymer having the formula HO-Dl-O - [-CO-AAl-C0-0-D1-0-] x-CO-AAl -CO-OM- (O-CO-AA1-C0-0-D1-0- [CO-AA1-C0-0-AD] y-OH) ni, where O-D1-O represents diol functionality, CO- AA1-C0 represents di acid functionality aliphatic carboxylic, O-AD-O represents the polyamide diol functionality, χ and y are the numbers of each of the repeating units in the polymer, the numerical average molecular weight of the transformed polymer being greater than 4,000 g / mol. Method according to claim 14, characterized in that the starting polymer comprises the residual of a bis amide diol and the reagent is a polyacid or polyacid ester. Method according to claim 19, characterized in that the starting polymer comprises a first repeating unit represented by the structure - [H1-AA] - where H1 is -R-CO-NH-R-NH-CO-R- 0- or -R-NH-CO-R-CO-NH-R-0- where at each occurrence R is independently an aliphatic or heteroaliphatic, alicyclic or heteroalicyclic or aromatic or heteroaromatic group and AA is -CO-R'-CO0-0 - where R 'is an aliphatic group and a second repeating unit having the structure - [R-0-AA] - where R is as defined above and the polyacid or polyacid ester is represented by the formula M (COOR1) n, where M is a n-valent organic portion and η is an integer of 3 or more and R1 is hydrogen or an aliphatic group of 1-10 carbon atoms. Method according to claim 20, characterized in that the branched polymer comprises the following repeating units: - [Hl-AA] -, - [RO-AA] -, and -M- (CO-OR) η . Method according to claim 20, characterized in that the starting polymer is represented by the formula HO-D1-O - [- C0-AA1-C0-0-D1-0-] x- [C0-AA1-C0 -0-AD] y-OH, where O-D1-O represents a diol functionality, C0-AA1-C0 represents a short aliphatic dicarboxylic acid functionality, O-AD-0 represents a short symmetrical diolcrystallized polyamide functionality, the mean-molecular weight of the polymer being less than 2,000 g / mol, and comprising: contacting the polymer with a polyacid ester having the formula M- (CO-OR) n to form a mixture, where η is 3 or more, the temperature of the mixture being sufficiently high to produce a transformed material comprising a transformed polymer having the formula H0-D1-0 - [- C0-AA1-C0-0-D1-0-] x-C0-M - (- C0-0-D1-0- [C0- AA1-C0-0-AD] y-OH) ni, where O-D1-O represents diol functionality, C0-AA1-C0 represents aliphatic dicarboxylic acid functionality, O-AD-O represents polyamide dio functionality. 1, χ and y are the numbers of each of the polymer repeat units, the numerical average molecular weight of the transformed polymer being greater than 4,000 g / mol. Method according to claim 14, characterized in that the starting polymer comprises a residual diester bis amide and the reagent is a polyol. Method according to claim 23, characterized in that the starting polymer comprises a first repeating unit represented by the structure - [H2-D] - and a second repeating unit represented by the structure - [D-AA] - where H2 is -C0-R-CO-NH-R-NH-CO-R-CO-O, D is - [RO] - and AA is -C0-R'-CO0-0- where R 'is an aliphatic group and R is an aliphatic or heteroaliphatic, alicyclic or heteroalicyclic or aromatic or heteroaromatic group and the polyol is represented by the formula M (OH) n, where M is an n-valiant organic moiety and η is an integer greater than or equal to 3. Method according to claim 24, characterized in that the branched polymer comprises the following repeating units: - [H2-D] -, - [R-O-AA] -, and -M- (AA) 11- · Method according to claim 24, characterized in that the starting polymer has the formula HO-D1-O- [-CO-AA1-CO-O-D1-O-Ix- [0-D1-0-C0 -DD-C0] y-OH, where O-D1-O represents a diol functionality, C0-AA1-C0 represents a short aliphatic acid dicarboxylic functionality, O-CO-DD-CO-O represents crystallized, symmetrical diacid diamide functionality, χ y and y are the numbers of each of the repeating units in the polymer, the number average molecular weight of the polymer being less than 2,000 g / mol, and comprising: contacting the polymer with a polyol having the formula M- (OH) n to form a mixture where η is greater than or equal to 3, the temperature of the mixture is sufficiently elevated to produce a transformed material comprising a transformed polymer having the formula HO-D1-O - [- C0-AA1-C0-0-D1-0-] x-C0 -AAl-CO-0-M- (0-CO-AA1-CO-O-O-D1-O- [0-D1-0-CO-DD-C0] y-OH) ni, where O-D1-O represents diol functionality, C0-AA1-C0 represents functionality aliphatic dicarboxylic acid, C0-AA1-C0 represents the functionality aliphatic dicarboxylic acid, O-CO-DD-CO-O represents the diacid diacid functionality, χ and y are the numbers of each repeating unit in the polymer, the average molecular weight of the transformed polymer being greater than 4,000g / mol. Method according to claim 14, characterized in that the starting polymer comprises the residual of a diester bis amide and the reagent is a polyacid or polyacid ester. Method according to claim 26, characterized in that the starting polymer comprises a first repeating unit represented by the structure - [H2-D] - and a second repeating unit represented by the structure - [D-AA] - where H2 is -CO-R-CO-NH-R-NH-CO-R-CO-O, D is - [RO] -, and AA is -CO-R'-C0-0- where R 'is an aliphatic group and R is an aliphatic or heteroaliphatic, alicyclic or heteroalicyclic or aromatic or heteroaromatic group and the polyacid or depolyacid ester has the formula M (COORl) n, where M is an n-valiant organic moiety and η is an integer greater than or equal to 3 and R1 is hydrogen or an aliphatic group of 1-10 carbon atoms. Method according to claim 27, characterized in that the branched polymer comprises the following repeating units: - [H2-AA] -, - [R-O-AA] -, and -M- (C00R) n-. Method according to claim 27, characterized in that the starting polymer has the formula HO-D1-O - [-CO-AA1-C0-0-D1-0-] x- [0-D1-0- C0-DD-C0] y -OH, where O-D1-O represents a diol functionality, -C0-AA1-C0 represents a short aliphatic acid dicarboxylic acid functionality, O-CO-DD-CO-O represents crystallized diacid diamide functionality, symmetric short, χ and y are the numbers of each of the repeating units in the polymer, the numerical average molecular weight of the polymer being less than 2,000 g / mol, and understanding the step of: contacting the polymer with a polyacid ester having the formula M- (CO- OR) n to form a mixture, where η is greater than or equal to 3, the temperature of the mixture being sufficiently high to produce a transformed material comprising a transformed polymer having the formula HO-D1-O - [- C0-AA1-C0-0-D1 -0-] x-CO-M - (-CO-0-D1-0- [0-DI-0-CO-DD-CO] y-OH) ni, where O-DL-O represents diol functionality, C0-AA1-C0 represents functionality aliphatic dicarboxylic acid, 0-CO-DD-CO-0-0 represents diacid diacid functionality, χ and y are the numbers of each of the nopolymer repeating units, the numerical average molecular weight of the transformed polymer being greater than 4,000 g / mol. Method according to any one of claims 1-7 and 14-22, characterized in that the residual polyolide diol has the formula - (CH 2) n -CONH- (CH 2) m - (X) (CH 2) m -CONH- (CH 2) n, wherein X = NH, O, S, k = 0 or 1, m = 1-4; and η = 4-6. Method according to any one of claims 1-7 and 14-22, characterized in that the residual short symmetrical diol polyamide functionality has the formula - (CH 2) n -CONH- (CH 2) m -CO-NH- ( CH 2) n, where n = 2-4 and m = 2-4. A method according to any one of claims 1-7 and 14-22, characterized in that the short symmetrical diol polyamide functionality has the formula -CO- (CH2) m-CO-NH- (CH2) k-NH- CO- (CH 2) m -CO-, where m = k = 2-4. A method according to any one of claims 1-30, characterized in that the short aliphatic dicarboxylic acid functionality is selected from the group consisting of succinic acid, glutaric acid and adipic acid; and the symmetric diol polyamide functionality has a formula selected from the group consisting of (CH2) n -CONH- (CH2) m- (X) k- (CH2) m-CONH- (CH2) n, wherein X = NH, O, S, k = 0 or 1, m = 1-4 and n = 4-6; - (CH 2) n -NH-CO- (CH 2) m -CO-NH- (CH 2) n -, where n = 2-4 and m = 2-4; and -CO- (CH 2) m -CO-NH- (CH 2) k -NH-CO- (CH 2) m -CO-, where m = k = 2-4. A method according to any one of claims 1-30, characterized in that the short aliphatic carboxylic acid functionality is selected from the group consisting of succinic acid, glutaric acid and adipic acid; the high boiling point diacid functionality is selected from the group consisting of azelaic acid and sebacic acid; and the short symmetric polyamidiol functionality has a formula selected from the group consisting of - (CH2) n-CONH- (CH2) m- (X) k- (CH2) m-CONH- (CH2) n, where X = NH, 0 S, k = 0 or 1, m = 1-4 and n = 4-6; - (CH 2) n -NH-CO- (CH 2) m -CO-NH- (CH 2) n -, where n = 2-4 and m = 2-4; e-CO- (CH 2) m -CO-NH- (CH 2) k -NH-CO- (CH 2) m -CO-, where m = k = 2-4. A method according to any one of claims 1-30, characterized in that the diolderivative functionality of a diol selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol . A method according to any one of claims 1-30, characterized in that the diolderivative functionality of a diol having a molecular weight greater than that of 1,6-hexanediol. A method according to any one of claims 14-18 and 23-26, wherein the selected polyol from the group consisting of glycerine, trimethylolpropane, methyl glycoside, sorbitol, a polyol polyol, and a soybean polyol. Polymer, characterized in that it is prepared by the method as defined by any one of claims 14-30. Polymer according to claim 39, characterized in that it has the formula HO-D1-O - [- C0-AA1-C0-0-D1-0-] x-CO-AA1-CO-OM- ( O-C0-AA1-C0-0-D1-0- [C0-AA1-C0-0-AD] y-OH) ni, where O-D1-O represents diol functionality, C0-AA1-C0 represents acid functionality. aliphatic dicarboxylic, O-ADD-O represents short symmetric crystallized diol polyamide functionality, M represents a polyetherivative functionality of a polyol having the formula M- (OH) 11, where η is greater than or equal to 3, and χ and y are the numbers each of the repeating units in the polymer. Polymer according to claim 40, characterized in that the polyolderivative functionality of a polyol selected from the group consisting of glycerin, trimethylolpropane, methyl glycoside, sorbitol, a polyether polyol, and soy polyol. Polymer according to Claim 39, characterized in that it has the formula HO-DI-O- [CO-AA1-CO-0-1-O-] x-CO-PA- (-C0-0- D1-0- [C0-AA1 -C0-0-AD] y-OH), where PA is derived from a polyacid ester having the formula PA- (CO-OR) n, where η is greater than or equal to 3, 0-Dl-O represents a diol functionality, C0-AA1-C0 represents a short dicarboxylic aliphatic acid functionality, O-AD-O represents a short symmetric crystallized diol polyamide functionality, χ and y are the numbers of each of the polymer repeat units, the weight number average molecular weight of the transformed polymer being greater than 4,000 g / mol. Polymer according to claim 39, characterized in that it has the formula HO-D1-O- [CO-AA1-C0-0-D1-0-] x-CO-AA1-CO-OM- (0 -C0-AA1-C0-0-D1-0- [0-D1-0-C0-DD-C0] y-OH) ni, where O-D1-O represents a diol functionality, C0-AA1-C0 represents a functionality short aliphatic dicarboxylic acid, 0-CO-DD-CO-O represents a short symmetric diacid crystallized diamid functionality, M represents a diol functionality derived from a polyol having the formula M- (OH) n, where η is greater than or equal to 3, χ and y are the numbers of each of the polymer repeat units. Polymer according to claim 43, characterized in that the polyolderivative functionality of a polyol selected from the group consisting of glycerin, trimethylolpropane, methyl glycoside, sorbitol, a polyether polyol, and soy polyol. Polymer according to claim 39, characterized in that it has the formula HO-D1-O - [-CO-AA1-C0-0-D1-0-] x-CO-PA- (C0-0- D1-0- [0-D1-C0-DD-C0] y-OH) n_i, where PA is derived from a polyacid ester having the formula PA- (CO-OR) n, where η is greater than or equal to 3 .0-Dl-O represents a diol functionality, C0-AA1-C0 represents a short dicarboxylic aliphatic acid functionality, O-CO-DD-CO-O represents a crystallized, symmetrical diacid short functionality, χ and y are the numbers of each of the repeating units. in the polymer, the number average molecular weight of the transformed polymer being greater than 4,000 g / mol.